EP0897267B1 - Animal feeds comprising chromium(iii) and manganese(ii) salts of short chain fatty acids - Google Patents
Animal feeds comprising chromium(iii) and manganese(ii) salts of short chain fatty acids Download PDFInfo
- Publication number
- EP0897267B1 EP0897267B1 EP98904772A EP98904772A EP0897267B1 EP 0897267 B1 EP0897267 B1 EP 0897267B1 EP 98904772 A EP98904772 A EP 98904772A EP 98904772 A EP98904772 A EP 98904772A EP 0897267 B1 EP0897267 B1 EP 0897267B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chromium
- salts
- iii
- reaction
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical class [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 241001465754 Metazoa Species 0.000 title claims description 27
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 title abstract description 19
- 150000004666 short chain fatty acids Chemical class 0.000 title abstract description 6
- 235000021391 short chain fatty acids Nutrition 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 235000005911 diet Nutrition 0.000 claims description 10
- 230000037213 diet Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009469 supplementation Effects 0.000 abstract description 5
- 150000007942 carboxylates Chemical class 0.000 abstract description 4
- 235000016709 nutrition Nutrition 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000003638 chemical reducing agent Substances 0.000 description 32
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 24
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 23
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- 239000008103 glucose Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- 235000019260 propionic acid Nutrition 0.000 description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 9
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 241000282898 Sus scrofa Species 0.000 description 6
- 229940046374 chromium picolinate Drugs 0.000 description 6
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- PYXSPTLIBJZHQW-UHFFFAOYSA-K chromium(3+);propanoate Chemical compound [Cr+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O PYXSPTLIBJZHQW-UHFFFAOYSA-K 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 102000004877 Insulin Human genes 0.000 description 4
- 108090001061 Insulin Proteins 0.000 description 4
- 241000282887 Suidae Species 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- -1 chromium (III) short chain fatty acids Chemical class 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000013601 eggs Nutrition 0.000 description 4
- 229940125396 insulin Drugs 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical compound [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 244000144977 poultry Species 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910021654 trace metal Inorganic materials 0.000 description 3
- 201000009030 Carcinoma Diseases 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical class [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- 230000001684 chronic effect Effects 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 235000015872 dietary supplement Nutrition 0.000 description 2
- VVFQQFIFXHHOBY-UHFFFAOYSA-N dipotassium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium;dihydrate Chemical compound O.O.[K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O VVFQQFIFXHHOBY-UHFFFAOYSA-N 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 235000006109 methionine Nutrition 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 239000004470 DL Methionine Substances 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 206010022489 Insulin Resistance Diseases 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 235000019735 Meat-and-bone meal Nutrition 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 235000019742 Vitamins premix Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- XAQCJVGGJJFLPP-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium Chemical class N.N.O[Cr](=O)(=O)O[Cr](O)(=O)=O XAQCJVGGJJFLPP-UHFFFAOYSA-L 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006027 corn-soybean meal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004710 electron pair approximation Methods 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007407 health benefit Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003946 protein process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004455 soybean meal Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
- A23L33/165—Complexes or chelates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S426/00—Food or edible material: processes, compositions, and products
- Y10S426/807—Poultry or ruminant feed
Definitions
- the present invention relates to metal carboxylates and, more particularly, to chromium(III) and manganese(II) salts of short chain fatty acids. A method of making the same, such that there are only sub-part-per-billion amounts of these metals in other valent forms present in the resultant salts, and the salts are suitable for use as nutritional supplementation of living organisms with the organic metal salts.
- Trace metals appear to be essential elements in the diet of living organisms, necessary to promote good health and the proper function of many biochemical enzymatic reactions and transportation processes. Since food intake does not always supply the appropriate amounts of these trace metals, such as chromium, iron, copper, zinc, manganese, etc., dietary supplementation is used. This is not only true for humans but also for animals.
- the supplemental material provides trace metals in several forms, including the inorganic salts of the trace metals, metal amino acid complexes, metal-amino acid chelate complexes, metal proteinate complexes and metal polysaccharide complexes.
- Manganese (II) is associated with a number of enzymatic reactions, including those contributing to growth and maintenance of bone and connective tissue. According to a number of animal studies, supplementation to animal feed with these trace metals provides health benefits to agricultural animals such as swine, beef and poultry.
- the effect of chromium (III) in a diet has been investigated in several animal species. Particularly, it has been shown in several studies to improve daily gain in swine and pigs per litter in sows. It has been theorized that the effect of chromium is due to an interaction with insulin which allows the metabolism of energy to take place more efficiently.
- chromium (III) As noted, it has been found that the addition of chromium (III) to a diet can increase the utilization of energy in the diet by the animal. However, the chromium is only a benefit to the diet if the chromium is bioavailable. It is noted that inorganic forms of chromium have very little biological activity, and that chromium (VI) is both an inactive form of chromium as well as being toxic and carcinogenic (McDowell). It is also noted that chronic exposure to even trace levels of chromium (VI) increases rates of carcinoma.
- Glycolic acid is not recognized as a feed ingredient by the FDA. Residues of glycolic acid would exclude these salts from such use. Glycolic acid is also found to be a poor reagent in this process, because the reagent grade acid contains between thirty and forty three percent water. It is known that water in the reaction mixture of the process of Drew causes the reaction to not proceed to completion (US patent 2,615,031 to Stover). The amount of water added to the reaction mixture with the glycolic acid would be small, but it may still result in increased chromium(VI) residues in the product.
- the discovery relates to a process for producing a substantially pure (herein after defined as containing only undetectable amounts of the unreduced metal (Cr +6 ) or (Mn +7 ), respectively) trivalent (Cr +3 ) or divalent (Mn +2 ) salt of a carboxylic acid (a metal carboxylate) having a formula of M(CH 3 (CH 2 ) x COO - ) y , where M is the trivalent or divalent metal cation, manganese (Mn +2 ) or chromium (Cr +3 ) and x is zero or one or two or three or four, and preferably zero or one so that an acetate or propionate salt is made, and y is an integer equal to the cationic charge of M.
- the discovered process begins with the mixing of 1) a carboxylic acid of C 2 -C 6 and preferably C 2 -C 3 with: 2) a polyvalent metal (polyvalent shall be defined here to be valences of greater than +3 valence) of a metal selected from chromium(VI) or manganese(IV) as a salt; and, 3) adding "selected reducing agents", herein after defined as reducing agents that pass the three part test: a) the reducing agent must be able to drive the reaction to completion, b) reducing agent does not leave any residues that would be toxic when fed to the targeted biological organism; c) the excess reducing agent in the final product is acceptable at the levels found to be in the feed of the organism which is targeted to consume it.
- the answer to these three questions can be completion, b) reducing agent does not leave any residues that would be toxic when fed to the targeted biological organism; c) the excess reducing agent in the final product is acceptable at the levels found to be in the feed of the organism which is targeted to consume it.
- the answer to these three questions can be determined without undue experimentation by those of skill in the art.
- the preferred reducing agents are glucose or propylene glycol, resulting in a metal salt of a chain fatty acid with substantially no Chromium (VI) present in the resultant material. More particularly, the process of the present invention is the preparation of chromium (III) propionate by the reduction of sodium dichromate dihydrate with propylene glycol, or other suitable reducing agent, in the presence of propionic acid.
- feed stuff is used to describe a mixture of plant or animal material, such as grain or animal by-products, vitamins, minerals or other feed additive used to feed agricultural or domesticated animals.
- food stuff is used to describe any item which may be consumed by humans.
- food is defined as all food stuffs and feed stuffs.
- the discovered process begins with the mixing of 1) a carboxylic acid of C 2 -C 6 and preferably C 2 -C 3 with: 2) a polyvalent metal (polyvalent shall be defined here to be valences of greater than +3 valence) selected from chromium(VI) or manganese(IV) as a salt; and 3) adding "selected reducing agents", hereinafter defined as reducing agents that pass the three part test; a) the reducing agent must be able to drive the reaction to completion (preferably in less process results in a metal salt of a short chain fatty acid with substantially no Chromium (VI) or polyvalent metal present in the resultant material.
- the reaction may be tested for the presence of the polyvalent metal; if that metal is not present, then the reduction is complete. Alternatively, excess amounts of the reducing agent can be used to assure reduction. Residues can be tested by spectographic analysis of the resultant material and comparison with the targeted organisms' tolerance for the residue; or, alternatively, the material can be fed to animals in control studies to determine the toxicity. The last test can be readily established by referencing approved materials for foods or for feeds; alternatively, controlled animal studies can be run on the target animal.
- chromium (III) salt of the fatty acid acetate or propionate several components are used: 1) a chromium (III) component, 2) an anhydrous short chain fatty acid, and 3) a reducing agent.
- the molar ratio of fatty acid to chromium(III) should be 3:1; however, additional propionate may be added as solvent.
- the reducing agent must be adding in amounts sufficient to drive the reaction to completeness, and, if the reducing agent is the preferred propylene glycol, then there should be approximately 0.4 moles per mole of chromium(VI).
- the chromium (VI) component is selected from any of the alkali metal or alkali earth metal or ammonium dichromates or chromate.
- Such salts would have the form of M x (Cr 2 O 7 ) y or M x (CrO 4 ) y , where M is any cation, and x and y are such that the charges of the cations and anions are equal.
- These salts may be in any hydrous or anhydrous form.
- the preferred is sodium or potassium dichromate dihydrate, because of cost and ease of accessibility.
- chromate or dichromate is used, since in acid, the chromate converts.
- additional propionic or other fatty acid selected
- These salts may be in any hydrous or anhydrous form.
- the preferred is sodium or potassium dichromate dihydrate, because of cost and ease of accessibility.
- chromate or dichromate is used, since in acid, the chromate converts.
- additional propionic or other fatty acid selected may be required.
- the fatty acid component is selected based on its having a formula of at least stoichmetric amounts, and preferably excess stoichmetric amounts, of the following: (CH 3 (CH 2 ) x COOH), where x is zero or one or two or three or four, used to form a trivalent (Cr +3 ) or divalent (Mn +2 ) salt of a carboxylic acid (a metal carboxylate).
- x zero or one, so that an acetate or propionate salt is made, and the number of these acids per each metal is an integer equal to the cationic charge of M (the metal).
- Carboxylic acids of C 2 -C 6 are acetate, propionate, butyrate, and valerate respectively.
- Valerate is the least preferred.
- C 2 -C 3 acetate and propionate are used, as they evidence fewer undesirable traits for the consummation of the final product.
- the fatty acids are preferably in the neat or anhydrous form to avoid addition of water to the reaction. Water makes the reaction more susceptible to having undesirable polyvalent metals in the resultant material.
- Select reducing agents are defined as reducing agents that pass the three part test: a) the reducing agent must be able to drive the reaction to completion (preferably in less than 24 hours); b) reducing agent does not leave any residues that would be toxic when fed to the targeted biological organism (particularly humans or agricultural animals); c) the excess reducing agent in the final product is acceptable at the levels found to be in the feed of the organism which is targeted to consume it.
- the preferred reducing agents are glucose or propylene glycol; however, it is thought that other mono, di or poly-saccharides such as fructose or sucrose may also act as adequate reducing agents for the purposes of this reaction. Likewise, other glycols may be useful if they pass the three- part test.
- the researcher should evaluate the selected reducing agents based on availability, price, and where the metal is being over-reduced. For example, glucose is less preferred than propylene glycol, because glucose can turn brown and form Chromium (II) which, in the oxidized form, is totally non-bioavailable to animals.
- the reaction temperature should be under control to avoid excessive heat from this exothermic reaction. Presently suggested are reaction times of twenty minutes to 24 hours, the preferred range being 1-3 hours. The reaction temperatures should be about 60 degrees C to -120 degrees C. Times greater than 24 hours can be employed, but they do not appear to be necessary, as the reaction goes to completion fairly rapidly.
- the product of this reaction is a solution of Chromium (III) in propionic acid. This mixture can be directly added to feed or sprayed on plant material or, alternatively, made into a dry form by adding a carrier such as silicon dioxide, cobmeal, calcium carbonate, vermiculite, bentonite and the like.
- Chromium(III) propionate was synthesized by the following reaction. In the laboratory runs a variable speed mechanical stirrer, a water cooled reflux condenser and a probe for determining the temperature of the reaction may have been employed. Heat was added where necessary by a heating unit.
- Propionic acid and sodium dichromate were mixed in a reaction vessel.
- the reaction mixture was heated to 900C.
- Glucose was added in small portions to the reaction mixture.
- large amounts of gas were produced by the mixture and the temperature of the mixture increased sharply to ⁇ 120-1350C.
- Propionic acid vapor was refluxed back into the vessel using a water cooled condenser. Portions of glucose were added until the reaction had gone to completion. The reaction time was -3 hours, but the time was dependent on how quickly the glucose is added. If the glucose were added in one portion, the reaction was complete within minutes. Upon further experimentation, it was found that the reaction was very slow until the reaction mixture was heated to 85-90°C.
- Propylene glycol could also be used as a reducing agent in place of the glucose. 499.73g propionic acid, 166.58g sodium dichromate, and 33.55g propylene glycol were reacted in a similar manner to the reaction above. The product was identical to that of the reaction using glucose as the reductant. Similarly to glucose, propylene glycol is acceptable as a feed additive.
- the three factors in the study will be feed energy, chromium level, and propionate level.
- the responses in this study will be eggs per hen per day, egg mass per hen per day, and feed intake per hen per day. From this data, feed-to-egg mass conversion will also be calculated.
- a high energy level feed at 1376 kcal/LB and a low energy level feed at 1097 kcal/LB were formulated per theoguidelines in Feed & Nutrition by Ensminger and Olentine, first edition.
- the two formulations were balanced for crude protein, methionine, and lysine content.
- the two formulations are listed in Table 1.
- the high chromium level will be 500ppb. No adjustment is necessary for the low level because only 5.67g of an 8% chromium product will treat one ton of feed at 500ppb.
- the high level of propionate will be one percent calcium propionate to the feed.
- One percent calcium carbonate will be added to the low propionate level treatment to keep the treatments balanced.
- the eight treatments are listed in Table 2. Treatment Energy Chromium Propionate 1 High High High 2 High High Low 3 High Low High 4 High Low Low Low 5 Low High Low 6 Low High Low 7 Low Low High 8 Low Low Low Low Low
- Each of the eight treatments will be fed to three randomly selected pens of eight or nine birds.
- the trial will last for 5 weeks.
- the hens will be given feed and water ad libitum for the duration of the trial.
- Feed intake and eggs per hen per day will be recorded daily throughout the trial.
- the weight of each days egg production will be recorded for each pen.
- the results of this study indicates the effect of bioavailable chromium on poultry.
- Ion chromatography using EPA method 218.6, was used to analyze a sample of chromium propionate prepared in the lab from sodium dichromate and a sample of Chromax - IOX (0.4% chromium picolinate). The analysis was done using Dionex equipment. No residual chromium(VI) could be detected in our product with a detection limit of 8.3 ppb, while chromium picolinate was found to contain 13 ppb. It must be noted that our product contained about 20 times the chromium of chromium picolinate. On an equal chromium basis, our product contain at least an order of magnitude less chromium(VI). A sample of high chromium yeast was also analyzed and found to contain 600 ppb chromium(VII).
- test 1 and 2 decreased P ⁇ .05 average daily gain and average feed intake per day, but not feed efficiency (p>. 10).
- Plasma from fasting swine showed neither source affected total cholesterol, urea, insulin, or HDL totals.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Food Science & Technology (AREA)
- Animal Husbandry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Nutrition Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
Description
Ingredient | High Energy Diet | Low Energy Diet |
Corn Meal | 64.00% | 56.00% |
Soybean Meal | 0.00% | 16.00% |
Corn Gluten Meal | 4.00% | 4.00% |
Meat and Bone Meal | 17.00% | 14.50% |
Poultry Fat | 5.50% | 0.00% |
Calcium Phosphate | 1.00% | 1.00% |
Limestone | 7.31% | 7.42% |
Salt | 0.30% | 0.30% |
L-Lysine | 0.15% | 0.05% |
DL-Methionine | 0.16% | 0.15% |
Trace Mineral Premix | 0.08% | 0.08% |
Vitamin Premix | 0.50% | 0.50% |
Treatment | Energy | Chromium | Propionate |
1 | High | High | High |
2 | High | High | Low |
3 | High | Low | High |
4 | High | Low | Low |
5 | Low | High | Low |
6 | Low | High | Low |
7 | Low | Low | High |
8 | Low | Low | Low |
Claims (1)
- A food composition for selectively supplementing essential trace metals in the diet comprising a metal salt of a fatty acid produced from an unreduced metal which is selected from manganese (Mn+7), and chromium (Cr+6) and is substantially pure of said unreduced metal, the metal salt of the fatty acid produced having the formula M(CH3 (CH2)xCOO-)y, where M is selected from manganese (Mn+2), and chromium, (Cr+3) and x is 0-4, and y is an integer equal to the cationic charge of M, and animal feed stuffs, wherein the composition contains an amount of said unreduced metal of less than 8.2 parts per billion.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US792000 | 1997-01-31 | ||
US08/792,000 US5846581A (en) | 1997-01-31 | 1997-01-31 | Chromium (III) salts of short chain fatty acids composition for use in animal feeds |
PCT/US1998/001782 WO1998033398A1 (en) | 1997-01-31 | 1998-01-30 | A process for the production of chromium(iii) salts of short chain fatty acids for use in animals feeds |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0897267A1 EP0897267A1 (en) | 1999-02-24 |
EP0897267A4 EP0897267A4 (en) | 2001-04-18 |
EP0897267B1 true EP0897267B1 (en) | 2005-03-16 |
Family
ID=25155495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98904772A Expired - Lifetime EP0897267B1 (en) | 1997-01-31 | 1998-01-30 | Animal feeds comprising chromium(iii) and manganese(ii) salts of short chain fatty acids |
Country Status (8)
Country | Link |
---|---|
US (1) | US5846581A (en) |
EP (1) | EP0897267B1 (en) |
AT (1) | ATE290796T1 (en) |
AU (1) | AU743959B2 (en) |
CA (1) | CA2256489C (en) |
DE (1) | DE69829339T2 (en) |
NZ (1) | NZ332280A (en) |
WO (1) | WO1998033398A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6197816B1 (en) * | 1998-09-30 | 2001-03-06 | University Of Alabama | Use of triaqua-mu3-oxohexakis-mu-propionatotrichromium (1+), [CR3O(O2CCH2CH3)6(H2O) 3]+, as a nutritional supplement or in treatment of medical conditions |
US6238708B1 (en) * | 1999-02-23 | 2001-05-29 | The Iams Company | Composition and process for controlling glucose metabolism in companion animals by dietary starch |
US7001618B1 (en) | 1999-07-09 | 2006-02-21 | The Iams Company | Nutritional composition for weight management |
US6630159B2 (en) * | 1999-02-23 | 2003-10-07 | The Procter & Gamble Company | Limiting weight gain of cats by feeding carbohydrate source that excludes rice |
JP2000333615A (en) * | 1999-05-28 | 2000-12-05 | Ajinomoto Co Inc | Mixed feed fortified with amino acid |
US6303158B1 (en) | 1999-08-04 | 2001-10-16 | Kemin Industries, Inc. | Chromium as an animal feed supplement |
US6525095B1 (en) | 2000-07-10 | 2003-02-25 | New Mexico State University Technology Transfer Corporation | Propionate feed supplement |
US6323354B1 (en) * | 2001-03-16 | 2001-11-27 | Agri-Nutrients Technology Group, Inc. | Amino acid chelates from lipoproteins |
US20060029642A1 (en) | 2004-08-03 | 2006-02-09 | Dusan Miljkovic | Methods and compositions for improved chromium complexes |
WO2006109194A2 (en) * | 2005-01-27 | 2006-10-19 | Ocean Nutrition Canada Ltd. | Chromium-fatty acid compounds and methods of making and using thereof |
US9968120B2 (en) | 2006-05-17 | 2018-05-15 | Dsm Nutritional Products Ag | Homogenized formulations containing microcapsules and methods of making and using thereof |
UA111815C2 (en) * | 2009-12-22 | 2016-06-24 | Ралько Ньютрішн, Інк. | ORGANIC CHELATED MINERAL COMPOSITIONS AND METHODS OF THEIR PREPARATION |
US8741375B2 (en) | 2011-06-07 | 2014-06-03 | Zinpro Corporation | Mixed amino acid metal salt complexes |
US8968807B1 (en) | 2013-09-24 | 2015-03-03 | Zinpro Corporation | Use of ethylene diamine metal complexes to deliver highly absorbable metals for animal nutrition |
UA117786C2 (en) | 2014-04-17 | 2018-09-25 | Ралко Нутрітіон, Інк. | Agricultural compositions and applications utilizing mineral compounds |
WO2016130981A1 (en) | 2015-02-13 | 2016-08-18 | Mars, Incorporated | Pet food feeding system |
WO2017070504A1 (en) * | 2015-10-23 | 2017-04-27 | Kemin Industries, Inc. | Method for reducing the viral load in poultry challenged with newcastle disease (nd)/ avian influenza (ai) |
BR112021019077A2 (en) * | 2019-03-27 | 2021-11-30 | Kemin Ind Inc | Methods for making one or more metal carboxylates and multiple metal carboxylates in a single reaction, and, metal carboxylate |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2650239A (en) * | 1952-04-18 | 1953-08-25 | Socony Vacuum Oil Co Inc | Preparation of chromic salts |
US2678328A (en) * | 1952-07-25 | 1954-05-11 | Socony Vacuum Oil Co Inc | Preparation of chromic salts |
SE371186B (en) * | 1971-01-04 | 1974-11-11 | Labofina Sa | |
GB1533061A (en) * | 1976-02-13 | 1978-11-22 | Graesser Salicylates Ltd | Preparation of chromium alkanoates |
US4315927A (en) * | 1980-08-08 | 1982-02-16 | The United States Of America As Represented By The Secretary Of Agriculture | Dietary supplementation with essential metal picolinates |
DE3215752A1 (en) * | 1982-04-28 | 1983-11-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING CALCIUM PROPIONATE |
US4636572A (en) * | 1985-03-11 | 1987-01-13 | Phillips Petroleum Company | Permeability contrast correction employing propionate-sequestered chromium(III) prepared by nitrite/dichromate redox |
US4764633A (en) * | 1987-08-31 | 1988-08-16 | Zinpro Corporation | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
US5061815A (en) * | 1988-07-06 | 1991-10-29 | Zinpro Corporation | Metal lysine complexes and method for producing metal lysine complexes |
US5336672A (en) * | 1992-07-21 | 1994-08-09 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Increasing egg production in poultry |
US5487772A (en) * | 1993-01-05 | 1996-01-30 | Mccoy; Paul E. | Carboxylate nutrients and methods for their production and use |
US5591878A (en) * | 1995-09-19 | 1997-01-07 | Kemin Industries, Inc. | Catalyzed process for producing metal carboxylates for use as animal feed supplements |
-
1997
- 1997-01-31 US US08/792,000 patent/US5846581A/en not_active Expired - Lifetime
-
1998
- 1998-01-30 EP EP98904772A patent/EP0897267B1/en not_active Expired - Lifetime
- 1998-01-30 DE DE69829339T patent/DE69829339T2/en not_active Expired - Lifetime
- 1998-01-30 AT AT98904772T patent/ATE290796T1/en not_active IP Right Cessation
- 1998-01-30 NZ NZ332280A patent/NZ332280A/en not_active IP Right Cessation
- 1998-01-30 WO PCT/US1998/001782 patent/WO1998033398A1/en active IP Right Grant
- 1998-01-30 AU AU62569/98A patent/AU743959B2/en not_active Expired
- 1998-01-30 CA CA002256489A patent/CA2256489C/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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ATE290796T1 (en) | 2005-04-15 |
DE69829339T2 (en) | 2006-04-06 |
CA2256489C (en) | 2005-09-27 |
AU743959B2 (en) | 2002-02-07 |
EP0897267A1 (en) | 1999-02-24 |
EP0897267A4 (en) | 2001-04-18 |
US5846581A (en) | 1998-12-08 |
NZ332280A (en) | 2000-02-28 |
DE69829339D1 (en) | 2005-04-21 |
AU6256998A (en) | 1998-08-25 |
WO1998033398A1 (en) | 1998-08-06 |
CA2256489A1 (en) | 1998-08-06 |
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